Models of Acid-Base Chemistry

Chapter 6

Friday, October 30, 2015

 Models of Acid-Base Chemistry
Several models have been developed to classify, rationalize and
predict the reactivity of acid-base pairs (or donor-acceptor pairs).

• Arrhenius Model – acids give hydrogen ions in aqueous solution

and bases give hydroxide in aqueous solution

• Brønsted-Lowry Model – acids are hydrogen ion donors and bases

are hydrogen ion acceptors

• Lewis Model – acids are electron pair acceptors and bases are
electron-pair donors

• Electrophile-Nucleophile Model – acids are electrophilic reagents

and bases are nucleophilic reagents

• Lux-Flood Model – acids are oxide (O2–) acceptors and bases are
oxide donors

• Usanovich Model – an acid-base reaction is a reaction leading to

formation of a salt
 Arrhenius Acid-Base Model
Acids form hydrogen ions in aqueous solution and bases form
hydroxide in aqueous solution

HCl aq   NaOH aq  

 NaCl aq   H 2O

HCl aq   H  Cl
 
acid
really more
like H3O+ NaOH aq   Na  OH
 
base

• Good fundamental definition of acids and bases for aqueous

solution
• Of limited use in non-aqueous solvents or the gas phase where
dissociation doesn’t occur
• Also fails to capture analogous reactivity of substances that don’t
dissociate into H+ or OH–, e.g., what do you do about NH3?
 Brønsted-Lowry Model
Acids release hydrogen ions and bases take up hydrogen ions

HCl + H2O H3O+ + Cl-

acid base acid base
strong weak weaker very weak
• Conjugate acids and bases – when an acid gives up a hydrogen
ion, it forms the conjugate base
• Acid-base reactions always proceed to form the weaker acid/base
pair
• The Brønsted-Lowry Model accommodates non-aqueous solvents
and gas-phase reactions
 
NH  NH 
4  2NH 3
2
NH 3

   
NH 
 H  NH 3
4
NH 3
NH  H 
2  NH 3
NH 3

acid acid base base acid acid

 Solvent System Model
This model for acid-base reactivity was developed for solvents that
can dissociate into cations (acid) and anions (base)
• The classic example is water:

acid base
• Now we can say that sulfuric acid is an acid because it increases
the concentration of H3O+:

• On the other hand, ammonia is a base because it increases the

concentration of OH–:
 Solvent System Model
Many solvents dissociate to some degree:
14.0

pKion = -log Kion = -log([H3O+][OH-])

34.4
 The Lewis Concept
A base is an electron-pair donor and an acid is an electron-pair
acceptor
• This model is consistent with the Arrhenius and Brønsted-Lowry
Models:

acid base
H   : NH 3 
 NH 4
Lewis Lewis
Acid Base

• It also works with molecules that neither give up nor accept a

hydrogen ion
BF3  : NH 3 
 H 3 N : BF3
Lewis Lewis Lewis
Acid Base Adduct
 The Lewis Concept
The Lewis concept also allows us to describe coordination complexes
within an acid-base framework.

Ag+ + 2 :NH3
Lewis Lewis
Acid Base
Coordinate covalent or dative bond –
used to show that both electrons in the
bond come from a Lewis base

• Lewis Acid-Base adducts in which the Lewis acid is a metal ion are
typically called coordination compounds
 The Lewis Concept and Molecular Orbitals
The Lewis concept of acids and bases is readily interpreted using
molecular orbital theory.

BF3  : NH 3 
 H 3 N : BF3

N–B σ*

LUMO

driving force
HOMO for adduct
formation An acid-base reaction
occurs when HOMO of
the base and LUMO of
N–B σ the acid combine to
create new HOMO and
LUMO in the product
 The Lewis Concept and Molecular Orbitals
The MO perspective on Lewis acids/bases is versatile and can help us
understand many types of reactions. Consider water:

water as oxidizing agent

3d

4s
large ΔE favors
electron transfer
LUMO (mostly on H’s)

HOMO (O 2py)

H2O Ca

Here, water acts as an “extreme Lewis acid” to oxidize Ca to Ca2+ (complete electron transfer)
2 H2O + Ca  Ca2+ + 2 OH- + H2
 The Lewis Concept and Molecular Orbitals
The MO perspective on Lewis acids/bases is versatile and can help us
understand many types of reactions. Consider water:

solvation of an anion

similar E favors
strong adduct 4s
LUMO
3p

HOMO

H2O Cl-

Here, water acts as a Lewis acid to form an adduct with an anion

n H2O + Cl-  [Cl(H2O)n]-

 The Lewis Concept and Molecular Orbitals
The MO perspective on Lewis acids/bases is versatile and can help us
understand many types of reactions. Consider water:

solvation of a cation

LUMO

similar E favors
strong adduct
HOMO
3s

2p

H2O Mg2+

Here, water acts as a Lewis base to form an adduct with a metal cation

6 H2O + Mg2+  [Mg(H2O)6]2+

 The Lewis Concept and Molecular Orbitals
The MO perspective on Lewis acids/bases is versatile and can help us
understand many types of reactions. Consider water:

water as reducing agent

LUMO

large ΔE favors
HOMO electron transfer

σu*

πg*
H2O F2

Here, water acts as an “extreme Lewis base” to reduce F2 to 2 F- (complete transfer)

2 H 2O + 2 F 2  4 F - + 4 H + + O 2
 HSAB Model
The Hard-Soft Acid-Base concept seeks to understand the reactivity of
Lewis acids and bases according to the polarizability of their valence
electrons (i.e., their deformability by other molecules/ions).
• hard Lewis acids are small acids with a high positive charge
• soft Lewis acids are larger and typically have a lower positive
charge

Hard Acids Borderline Acids Soft Acids

H+, Li+, Na+, K+ BH3, Tl+, Tl(CH3)3

Be2+, Mg2+, Ca2+, Sr2+ Cu+, Ag+, Au+, Cd2+,
B(CH3)3
BF3, BCl3, B(OR)3 2+ 2+ 2+ Hg22+, Hg2+, CH3Hg+
Fe , Co , Ni
Al3+, AlCl3, AlH3 2+ 2+ [Co(CN)5]2–, Pd2+, Pt2+
Cu , Zn
Cr3+, Mn2+, Fe3+, Co3+ 3+, Ir3+, Ru3+, Os2+ Br2, I2
Rh
Mn+ (n ≥ 4) Mn+ (n = 0)
H-bonding molecules π-acceptor molecules
 HSAB Model
The Hard-Soft Acid-Base concept seeks to understand the reactivity of
Lewis acids and bases according to the polarizability of their valence
electrons (i.e., their deformability by other molecules/ions).
• hard Lewis bases are small bases with highly electronegative
donor atoms
• soft Lewis bases are larger and typically have smaller
electronegativities

Hard Bases Borderline Bases Soft Bases

H–
F–, Cl– I–
H2O, OH–, O2–, ROH, Br– H2S, SH–, S2–, RSH,
RO–, R2O, RCOO– NO2–, N3– RS–, R2S
NO3–, ClO4–, CO32–, SO32– SCN–, CN–, RNC, CO
SO42–, PO43– C6H5NH2, C5H5N, N2 S2O32–
NH3, RNH2, N2H4 PR3, P(OR)3, AsR3,
C2H4, C6H6, R-
 HSAB Theory
The Hard-Soft Acid-Base concept seeks to understand the reactivity of
Lewis acids and bases according to the polarizability of their valence
electrons (i.e., their deformability by other molecules/ions).
• hard Lewis acids are small acids with a high positive charge, soft
Lewis acids are larger and typically have a lower positive charge
• hard Lewis bases are small bases with electronegative donor
atoms, soft Lewis bases are larger and typically have smaller
electronegativities

Hard acids prefer to interact with hard bases, soft acids prefer to
interact with soft bases.

 Zn C4 H 9 2 Li2O

ZnO  2LiC4 H 9 
borderline acid hard acid borderline acid hard acid
hard base soft base soft base hard base
 HSAB Theory and Exchange Reactions
HSAB theory is consistent with the large differences in Keq for simple
exchange reactions:

Hg2+ is a soft acid. As the halide becomes softer, the reaction becomes
increasingly favorable.
 HSAB Theory and Solubilities
Because the dissolution of salts in water typically requires the
replacement of a Lewis base with water, HSAB can predict trends in
solubilities. Consider the silver halides:

• F– and Cl– are hard bases; however, so is water. It turns out that
water is softer than F– but harder than Cl–
• Br– and I– are soft bases
• Because Ag+ is a soft acid, it is less prone to give up the halide as
we move down the series
 HSAB Theory and Solubilities
Because the dissolution of salts in water typically requires the
replacement of a Lewis base with water, HSAB can predict trends in
solubilities. Lithium halides show the opposite trend:

• F– and Cl– are hard bases; however, so is water. It turns out that
water is softer than F– but harder than Cl–
• Br– and I– are soft bases
• In this case, Li+ is a hard acid and it prefers to interact with the
hardest base available
 HSAB Theory and Metal Thiocyanate Complexes
In coordination complexes the metal is the Lewis acid. The Lewis base
is normally called a ligand.
• Thiocyanate (SCN–) is an interesting ligand because there are two
Lewis base sites:

“linkage isomerism”
 Pearson’s Absolute Hardness Scale
The absolute hardness is defined as

IA

2
• I is the ionization energy of the molecule in eV, approximately
equal to -EHOMO
• A is the electron affinity of the molecule in eV, approximately equal
to -ELUMO
• So the absolute hardness is just half the HOMO-LUMO difference
(i.e., half the band gap!)

• Hard acids have large values for η, soft acids have smaller values
for η

• Softness of a donor atom is given by the inverse of hardness, i.e.,

1


Pearson’s Absolute Hardness Scale
 The Nature of the Adduct

Hard acid/hard base adducts tend to have more ionic character

in their bonding. These are generally more favored energetically.

Soft acid/soft base adducts are more covalent in nature.

 Acid/Base Strength
It is important to realize that hard/soft considerations have
nothing to do with acid or base strength. An acid or a base may
be hard or soft and also be either weak or strong.

In a competition reaction between two bases for the same acid,

one must consider both the relative strength of the bases, and
the hard/soft nature of each base and the acid.

 Zn C4 H 9   Li2O
ZnO  2LiC4 H 9 
2
borderline acid hard acid borderline acid hard acid
hard base soft base soft base hard base

Zinc ion is a strong Lewis acid, and oxide ion is a strong Lewis base,
suggesting the reaction is unfavorable as written.
However, the reaction proceeds to the right (K > 1), because hard/soft
considerations override acid-base strength considerations.
 Drago’s EC Approach
A quantitative system for calculating the thermodynamics of acid-base
reactions takes account of both covalent and ionic components of the
acid-base interaction. For the reaction,

• EA and EB are the capacity for electrostatic (ionic) interactions of

the acid and base
• CA and CB are the capacity for covalent interactions of the acid and
base

• I2 is the reference acid with CA = EA = 1.00 kcal/mol

• Reference bases are MeC(O)NMe2 (EB = 1.32) and SEt2 (CB = 7.40)
 Using the EC Model
The enthalpy of a given Lewis acid-base reaction can be determined
using tabulated values (see Table 6.17 in your textbook).

Lewis Lewis Lewis

acid base adduct

H  EA EB  C AC B

 kcal   kcal   kcal   kcal 

H   1.00  0.525 
  1.00  0.681 
 mol   mol   mol   mol 
kcal
H  1.21 within 9% of experimental value
mol
 Summary
• There are several models to describe acids and bases. The Lewis
model is one of the most general since it does not depend on the
transfer of a hydrogen ion.

• A dative bond (coordinate covalent bond) is often used to denote a

bond between a neutral Lewis base and a Lewis acid:

• The Lewis model is readily interpreted using MO theory: the HOMO

of the Lewis base interacts with the LUMO of the Lewis acid.

• HSAB provides a semi-quantitative method for understanding

trends in acid-base reactivity: hard acids like hard bases and soft
acids like soft bases.

• The Drago EC model provides a more quantitative method for

understanding the thermodynamics of an acid-base reaction.